WO2018054212A1 - Composite de graphène, son procédé de préparation et son utilisation, procédé de préparation de nanocellulose et nanocellulose résultante, et nanocellulose composite de graphène à haute performance et son procédé de préparation - Google Patents

Composite de graphène, son procédé de préparation et son utilisation, procédé de préparation de nanocellulose et nanocellulose résultante, et nanocellulose composite de graphène à haute performance et son procédé de préparation Download PDF

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WO2018054212A1
WO2018054212A1 PCT/CN2017/100249 CN2017100249W WO2018054212A1 WO 2018054212 A1 WO2018054212 A1 WO 2018054212A1 CN 2017100249 W CN2017100249 W CN 2017100249W WO 2018054212 A1 WO2018054212 A1 WO 2018054212A1
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graphene
nanocellulose
group
cellulose
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PCT/CN2017/100249
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English (en)
Chinese (zh)
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唐一林
张金柱
王鹏辉
郑应福
许日鹏
刘顶
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济南圣泉集团股份有限公司
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Priority claimed from CN201610835479.XA external-priority patent/CN106832425A/zh
Priority claimed from CN201611143799.5A external-priority patent/CN106832426A/zh
Priority claimed from CN201611160905.0A external-priority patent/CN106829944B/zh
Application filed by 济南圣泉集团股份有限公司 filed Critical 济南圣泉集团股份有限公司
Publication of WO2018054212A1 publication Critical patent/WO2018054212A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment

Definitions

  • the invention relates to the field of nano materials, in particular to a graphene composite, a preparation method thereof and use thereof, a method for preparing nano cellulose, a obtained nano cellulose, a high performance graphene composite nano cellulose and a preparation method thereof .
  • Graphene is a two-dimensional material of a honeycomb structure composed of a single layer of sp2 hybridized carbon atoms, and has many excellent properties. Since its discovery in 2004, graphene has become a research hotspot in the scientific community. While studying the physicochemical properties of graphene, graphene-related composite materials are also emerging. In the direction of nanoscience, graphene is also used to prepare related nanocomposites, especially graphene/metal or graphene/metal oxide nanocomposites. Due to the excellent properties of graphene, these nanocomposites have broad research prospects in new energy, biosensing, catalysis, optical materials and other fields.
  • Graphene on the market is generally divided into powders and slurries.
  • powders strong ultrasound is required before application, and even dispersants are needed to assist dispersion.
  • slurry the situation is slightly better, but ultrasound is also required before use, and there will also be a dispersant in the dispersion.
  • the graphene is generally modified or a better dispersant is selected, or the graphene concentration is as low as possible, and the concentration of the graphene slurry on the market is generally 0.5 wt%. Below, otherwise the dispersion effect will be poor and precipitation will occur easily. This not only increases transportation costs, but also causes a large amount of solvent contamination, and requires removal of the dispersion during downstream applications, which inevitably increases process complexity and cost.
  • Nanocrystalline cellulose is a widely existing and renewable resource on earth.
  • the nanocrystalline cellulose is a cellulose crystal obtained by removing the amorphous region and the low crystallinity crystalline region in the cellulose after the natural cellulose is treated (for example, acid hydrolysis, biological enzymatic hydrolysis, etc.).
  • Nanocrystalline cellulose prepared from natural cellulose not only has the basic structure and properties of cellulose, but also has a large specific surface area, high crystallinity (>70%), high hydrophilicity, high Young's modulus, high strength. (7500MPa), ultra-fine structure and high transparency, good biodegradability and biocompatibility as well as stable chemical properties.
  • nano-microcrystalline cellulose has great potential for chemical modification, which promotes its application in papermaking, medicine, food, composite materials and other fields. It’s hot.
  • a graphene composite comprising a graphene composite mainly composed of nanocellulose and graphene, wherein nanocellulose At least a portion is interposed between the graphene species.
  • the graphene-based substance includes a mixture of one or more of graphene, biomass graphene, graphene oxide, and graphene derivatives.
  • Graphene is a layered structure or a pleated sheet structure, and the sheet size is on the order of nanometers, because of the intermolecular force, it is easy to cause agglomeration.
  • Nanocellulose is also nano-scale, but has a long-to-diameter ratio, which is equivalent to a rod-like structure. When two different nanomaterials are mixed together, it is generally believed that they will still reunite.
  • the present inventors have unexpectedly found that nanocellulose and graphene-like substances are sufficiently dispersed, and the obtained graphene composite is very easily dispersed in a liquid without using an ultrasonic or dispersing agent.
  • the diameter of the nanocellulose is smaller than the diameter of the graphene-based material. Without being bound by theory, it is believed that during the mixing of the two, the small diameter of the nanocellulose is easily inserted between the graphene sheets, and the graphene is weakened by the length of the nanocellulose, which weakens the graphene sheet. The intermolecular forces between the layers make the graphene-based materials easy to disperse later after agglomeration.
  • the number of layers of the graphene is 1-10 layers; preferably, the graphene is selected from one of single layer graphene, double layer graphene, and a few layers of graphene having 3-10 layers or A variety.
  • the biomass graphene is a monolayer graphene, a small layer graphene, a graphene nanosheet layer structure prepared by a catalytic or carbonization process using biomass resources as a main raw material, and is loaded with metal/non-metal.
  • a composite carbon material of a metal compound is a monolayer graphene, a small layer graphene, a graphene nanosheet layer structure prepared by a catalytic or carbonization process using biomass resources as a main raw material, and is loaded with metal/non-metal.
  • a composite carbon material of a metal compound is a monolayer graphene, a small layer graphene, a graphene nanosheet layer structure prepared by a catalytic or carbonization process using biomass resources as a main raw material, and is loaded with metal/non-metal.
  • the graphene derivative comprises any one or a combination of at least two of elemental doped graphene or functionalized graphene.
  • the graphene derivation comprises any one or a combination of at least two of elemental doped graphene or functionalized graphene.
  • the element doped graphene comprises any one or a combination of at least two of metal doped graphene or non-metal element doped graphene.
  • the metal element in the metal doped graphene comprises potassium, sodium, gold, silver, iron, copper, nickel, chrome titanium, vanadium or cobalt.
  • the non-metallic elements in the non-metallic element doped graphene include nitrogen, phosphorus, silicon, boron or silicon.
  • the non-metal element doped graphene comprises any one or a combination of at least two of nitrogen-doped graphene, phosphorus-doped graphene or sulfur-doped graphene.
  • the functionalized graphene comprises graphene grafted with a functional group.
  • the functionalized graphene includes graphene grafted with any one or a combination of at least two of a hydroxyl group, a carboxyl group or an amino group.
  • the hydroxyl group comprises R1-OH, and R1 is an alkyl group; preferably, the hydroxyl group is selected from the group consisting of methylhydroxyl, ethylhydroxyl, and propyl One or more of a hydroxy group, a butyl hydroxy group, a pentyl hydroxy group, and a hexyl hydroxy group.
  • the carboxyl group comprises R2-COOH, and R2 is an alkyl group; preferably, the carboxyl group is selected from the group consisting of methylcarboxyl, ethylcarboxy, propylcarboxy, butylcarboxy, pentylcarboxy, hexylcarboxyl One or more of them.
  • the amino group comprises R3-NH3, and the R3 comprises an alkyl group; preferably, the amino group is selected from the group consisting of methylhydroxyl, ethylhydroxy, propylhydroxy, butylhydroxy,pentylhydroxy,hexylhydroxyl One or more of them.
  • the graphene-based material is subjected to TEMPO catalytic oxidation treatment.
  • Graphene-based substances treated by the TEMPO catalytic oxidation system have more carboxyl groups added between the graphene sheets, and thus the intercalation effect of the nanocellulose is added to make the dispersion effect more excellent.
  • the TEMPO catalytic oxidation system comprises an aqueous solution system comprising TEMPO and/or a derivative thereof, hypochlorite or a bromide salt; more preferably TEMPO (2,2,6,6-tetramethylpiperidine)
  • the TEMPO derivative is selected from the group consisting of 2-azaadamantane-N-oxyl, 1-methyl-2-aza-adamantane-N-oxyl, 1,3-dimethyl-2-nitrogen
  • a heteroadamantane-N-oxyl group a 4-hydroxy TEMPO derivative.
  • the TEMPO and/or its derivative is added in an amount of 0.05 to 5% by weight, preferably 0.1 to 3%, more preferably 0.3% to 2%, still more preferably 0.5 to 1% by weight of the graphene-based substance; 0.1%, 0.3%, 0.8%, 1%, 1.2%, 1.5%, 2.5%, 3.5%, 4%, 4.5%, and the like.
  • the hypochlorite is added in an amount of 10 to 500%, preferably 30% to 90%, more preferably 40 to 75%, and may be 50%, 70%, 100%, 120%, by weight of the graphene-based substance. 135%, 160%, 200%, 300%, 400%, 450%, etc.
  • the chlorinated salt is added in an amount of 0.5 to 50%, preferably 10 to 30%, more preferably 3% to 20%, still more preferably 5% to 10%, and may be 3% or 8% by weight of the graphene-based substance. , 10%, 12%, 15%, 18%, 25%, 35%, 45%, etc.
  • TEMPO is a typical process for treating graphenes by mixing TEMPO and/or its derivatives with a halogen salt (such as a bromide salt such as NaBr), stirring and dissolving, then adding graphene to continue stirring, and then stirring.
  • a hypochlorite such as sodium hypochlorite solution is added to control the pH between 10-11.
  • the particle size of the graphene composite of the present invention is not critical, and of course, the smaller the particle size, the better.
  • the present invention splits the large particles into small particles by introducing nanocellulose, or interpolates the nanocellulose inside the large particles, which has weakened the agglomeration between the graphenes and is easily dispersed.
  • the graphene has a particle size of 50 ⁇ m.
  • the nanocellulose enters the interior of the particle, and the graphene sheet is disassembled to form a particle having a particle size of 30 ⁇ m.
  • nanofibers may still exist inside the 30 ⁇ m particle.
  • the graphene composite has a D90 of 30 ⁇ m or less, preferably 15 ⁇ m or less, preferably 10 ⁇ m or less, preferably 5 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.51 ⁇ m or less, further preferably 0.4 ⁇ m or less. Still more preferably 0.3 ⁇ m or less, and most preferably 0.2 ⁇ m or less.
  • the graphene composite particles have a D90 in the range of 0.001-30 ⁇ m, 0.01-25 ⁇ m, 0.015-20 ⁇ m, 0.02-15 ⁇ m, 0.03-10 ⁇ m, 0.04-9 ⁇ m, 0.05-8 ⁇ m, 0.06-6 ⁇ m, 0.07-5 ⁇ m, 0.08-3 ⁇ m, 0.09-1 ⁇ m, or 0.1-0.5 ⁇ m.
  • the content of nanocellulose in the graphene composite is within 10 wt%, preferably within 8 wt%, preferably within 5 wt%, preferably within 3 wt%, preferably within 1 wt%, preferably at 0.5. Less than wt%. According to some embodiments, the content of nanocellulose ranges from 0.1 wt% to 10 wt%, between 0.2 wt% and 8 wt%, between 0.3 wt% and 5 wt%, between 0.4 wt% and 3 wt%, 0.5 wt%. Between -2 wt% or 0.1 wt% - 1 wt%.
  • Nanocellulose is used as an additive for graphenes, and excessive addition is likely to cause side effects.
  • Nano-cellulose itself is a nano-material, which has a long-diameter ratio. If it is added in too much, it is easy to agglomerate itself. In addition, the diameter is small and the length is long. It is easy to form a entanglement to wrap the graphene-like substances together, but instead Adding the reaction of agglomeration, and thus controlling the amount of addition thereof, is also one of the innovations of the present invention.
  • the nanocellulose content of the invention is preferably controlled within 10 wt%, of course, the most preferred range is between 0.1 wt% and 1 wt%, the amount of nanocellulose added is small, and the problem of dispersion of graphene is solved. Affects downstream applications of graphene.
  • the nanocellulose is selected to have a diameter within 30 nm, preferably within 20 nm, more preferably within 10 nm, more preferably within 5 nm; and the aspect ratio of nanocellulose is (5-200):1, It is preferably (10-100): 1, more preferably (15-40): 1.
  • the length of the cellulose is too long, and the diameter is too small, which may cause the nanocellulose to adsorb on the surface of the graphene and lose its proper function.
  • the nanocellulose preparation raw material is derived from a crop such as corn cob, plant straw, cotton, and wood; preferably, the nanocellulose is a nanocellulose selected from the group consisting of corncob cellulose as a raw material;
  • the nanocellulose is prepared by purifying and bleaching corncob cellulose.
  • the present inventors have found that nanocellulose prepared by corncob cellulose has a better dispersion effect on graphene, especially for dispersing biomass graphene.
  • the invention further relates to a method for preparing a graphene composite comprising: dispersing nanocellulose and graphene in a solution into a suspension.
  • the method further comprises: removing the suspension from the solution, washing, and drying.
  • solution removal includes centrifugation, filtration, or a combination thereof.
  • the drying comprises vacuum drying, freeze drying, air flow drying, microwave drying, infrared drying, high frequency drying or a combination thereof.
  • the drying is freeze drying.
  • the dispersion is performed by one of high speed agitation or shearing, sonication, and grinding, or a combination thereof, preferably by dispersion, by sonication and milling.
  • the frequency of the milling is between 25 and 35 Hz, more preferably between 27 and 32 Hz, and the time of milling is controlled between 4 and 6 hours, more preferably between 5 and 5.5 hours.
  • the time of the ultrasonic dispersion treatment is from 15 to 60 min, more preferably from 30 to 50 min.
  • the power of the ultrasonic dispersion treatment is from 500 to 1500 kW, more preferably from 1,000 to 1,200 kW.
  • the graphene composite of the present invention can be obtained by physically blending graphene-based materials with nano-cellulose, but the effect is worse.
  • the solution itself also acts to disperse the graphene-like substance and the nano-cellulose, and it is easier to interpolate the nano-cellulose into the graphene material and increase Nanocellulose and graphene The number of collisions and the angle of collision are more conducive to the combination of the two.
  • the invention also relates to the use of graphene composites according to the invention in textiles, pharmaceuticals, environmental protection, food packaging, composite materials.
  • the invention also relates to a graphene composite nanocellulose with high performance, wherein the graphene material can maintain a high content, the graphene particles are still uniformly dispersed, the particle size is relatively uniform, and the agglomeration is achieved.
  • the particles are less produced, and the graphenes are added in the process of preparing the nanocellulose, so that the graphenes can be opened in the non-crystalline region of the cellulose and intercalated with the nanocellulose to achieve in-situ recombination, which is more effective.
  • Embodiments of the present invention provide a high-performance graphene composite nanocellulose product, which is mainly composed of a graphene-based substance and nano-cellulose, and the graphene-based substance and nano-cellulose are carried in situ with each other;
  • the content of the graphene-based substance is 20% by weight or less, further 10% by weight or less, and further preferably 0.5% by weight to 5% by weight.
  • the graphene composite nanocellulose has a graphene content of less than 20 wt%, because if the graphene content is too high, the graphene and the nanocellulose are easily separated, and the graphene particles are agglomerated in the nanocellulose.
  • the dispersibility is not good, which in turn affects the performance of the final product. Therefore, the content of graphene substances needs to be controlled within a suitable range to ensure excellent dispersibility. This range is also a comparison optimized by the inventors through a large amount of practical experience.
  • a suitable content more preferably, the content of the graphene-based substance is controlled to be 10% by weight or less, and may be between 0.5% by weight and 5% by weight, and other than, for example, 1% by weight, 1.5% by weight, 2% by weight, and 2.5% by weight. , 3.5 wt%, 4 wt%, and the like.
  • the graphene composite nanocellulose of the present invention has a relatively high graphene content, but the particle dispersion is relatively uniform, and additionally imparts excellent antibacterial properties, excellent toughness, hot water resistance and antistatic property to the nanocellulose material.
  • the raw material cost is low and the investment is small. This further expands the market application range of the fiber material, increases the added value of the product, and is also beneficial for further promotion and application.
  • the nanocellulose is prepared from corncob cellulose, and preferably, the nanocellulose is prepared by purifying and bleaching corncob cellulose.
  • the raw material for preparing nanocellulose of the present invention is preferably corncob cellulose, because corncob cellulose itself is equivalent to waste recycling, realizing reasonable redistribution of resources, and the use of such cellulose makes the prepared graphene composite nanometer.
  • Cellulose products have a more uniform particle size.
  • corncob cellulose to be purified and bleached prior to preparation of nanocellulose
  • the corncob raw material is subjected to acid hydrolysis, and the pentose sugar solution and the acid hydrolysis residue are obtained after separation; the acid used is a common acid solution such as sulfuric acid, hydrochloric acid, phosphoric acid, sulfurous acid, etc., and the amount of the acid is 1-10% by weight of the corncob raw material.
  • hydrolysis temperature is 100-150 ° C, time is 0.5-3h;
  • the above acid hydrolysis residue is treated with an alkali solution, and after separation, an alkali solution and an alkali residue are obtained.
  • the alkali used is sodium hydroxide, the amount of the base is 1-15 wt% of the corn cob raw material, the treatment temperature is 40-100 ° C, and the time is 1-6 h;
  • bleaching the above-mentioned alkaline residue which comprises one or more of sodium hypochlorite bleaching, hydrogen peroxide bleaching, alkali treatment, acid treatment and the like.
  • corncob cellulose After the above purification treatment, corncob cellulose can be obtained, and the main indexes are cellulose content: 80-95%, whiteness 70-90%, ash 0.1-2%, and fiber length 0.05-0.5 mm.
  • the aspect ratio of the nanocellulose is controlled to be (5-1000):1, preferably (10-300):1, more preferably (15-200):1.
  • the minimum diameter of the nanocellulose is less than 20 nm, preferably 10 nm or less, more preferably 5 nm or less.
  • the graphene-based substance used in the present invention includes one or a mixture of graphene, biomass graphene, graphene oxide, and graphene derivatives, and the graphene derivative is a modified graphene.
  • the graphene derivation comprises any one or a combination of at least two of elemental doped graphene or functionalized graphene.
  • the element doped graphene comprises any one or a combination of at least two of metal doped graphene or non-metal element doped graphene.
  • the metal-doped metal element typically, but not limited to, includes potassium, sodium, gold, silver, iron, copper, nickel, chrome titanium, vanadium or cobalt.
  • the non-metallic element doped graphene typically includes, but is not limited to, nitrogen, phosphorus, silicon, boron or silicon.
  • the non-metal element doped graphene comprises any one or a combination of at least two of nitrogen-doped graphene, phosphorus-doped graphene or sulfur-doped graphene.
  • the functionalized graphene comprises graphene grafted with a functional group.
  • the functionalized graphene comprises graphene grafted with any one or a combination of at least two of a hydroxyl group, a carboxyl group or an amino group.
  • the hydroxyl group of the present invention includes -R1-OH, and the R1 includes an alkane group, and a typical but non-limiting hydroxyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or the like. .
  • the carboxyl group of the present invention includes -R2-COOH, and the R2 includes an alkane group, and a typical but non-limiting hydroxyl group may be a methylhydroxy group, an ethylhydroxy group, a propylhydroxy group, a butylhydroxy group, a pentylhydroxy group, a hexylhydroxy group, or the like. .
  • the carboxyl group of the present invention includes -R3-NH3, and the R3 includes an alkane group, and a typical but non-limiting hydroxyl group may be a methylhydroxy group, an ethylhydroxy group, a propylhydroxy group, a butylhydroxy group, a pentylhydroxy group, a hexylhydroxy group, or the like. .
  • biomass graphene is a two-dimensional nanometer containing a single layer of graphene, a small layer of graphene, a graphene nanosheet layer structure, and supporting a metal/nonmetal compound with a layer number of not more than 10 layers.
  • the carbon material may even be a composite carbon material containing graphitized carbon or a metal/nonmetal compound on the basis of the above.
  • the invention also provides a preparation method of the above-mentioned high-performance graphene composite nanocellulose, wherein the preparation method has a close connection before and after, and the method is simple and quick, and no chemical agent such as acid and alkali is used in the whole preparation process, and the environment is green and there is no
  • the production of waste acid caustic soda, and the preparation method of the present invention also achieves the advantages of using acidification to prepare nanocellulose, such as a suitable aspect ratio.
  • the preparation method has the advantages of simple and easy operation, mild operating conditions, and industrialized production of graphene composite nanocellulose, and good economic benefits.
  • the invention also provides the above-mentioned application of high performance graphene composite nanocellulose, which is widely used and can be widely applied in various industries.
  • the present invention also provides a method for preparing the graphene composite nanocellulose, which comprises the following steps: (A) cellulose, graphene materials and Ionized water is mixed and ultrasonically dispersed and ground to obtain a suspension; (B) the suspension is ultrasonicated, centrifuged, and freeze-dried to obtain graphene composite nanocellulose.
  • the synthesis processes of nanocellulose mainly include the following:
  • MFC microfibrillated cellulose
  • NCC is a rigid rod-shaped cellulose having a diameter of 1 to 100 nm and a length of several tens to several hundreds of nanometers. It generally has a crystalline form of natural cellulose I and forms a stable suspension in water. Specifically, it includes enzymatic hydrolysis method, enzymatic hydrolysis method and biological method.
  • the preparation of NCC by enzymatic hydrolysis method produces a large amount of waste acid and impurities, which requires high reaction equipment, and the residue after reaction is difficult to recover, but the preparation process is relatively mature and has been realized. Industrial production.
  • Biological methods Cellulose prepared by microbial synthesis is commonly referred to as bacterial cellulose, and the physical and chemical properties of bacterial cellulose are similar to those of natural cellulose.
  • the preparation of NCC by biological methods can regulate the structure, crystal form and particle size distribution of NCC, and thus it is easy to realize industrialization and commercialization.
  • the preparation process of bacterial cellulose is complicated, time consuming, high in cost, expensive, and low in yield.
  • the mechanical method is prone to the problem of uneven particle size distribution.
  • the chemical method itself is not environmentally friendly, pollutes the environment, and has a certain degree of damage to the health of the operator.
  • the graphite of the present invention The preparation method of the olefin composite nanocellulose not only solves the problem of uneven distribution of mechanical particle size, but also avoids the problem of serious environmental pollution by using the chemical method, and the operation cost of the whole preparation method is relatively low.
  • the particle size index of the graphene-containing substance is also strictly required, and the D90 index of the graphene-based substance is controlled to be 70 ⁇ m or less, and the D10 index is controlled to be 20 ⁇ m or less.
  • graphene composite nanocellulose products only limited the graphene content, but neglected the important parameter of the particle size index of the graphenes themselves.
  • the inventors of the present invention have conducted a large number of creative experiments by using graphene. The content of the substance and the particle size index are limited to a suitable range, and the interaction of these indexes works together to finally achieve the object of the present invention, and the problem of uneven dispersion of the graphene particles is surely solved.
  • the D90 index of the graphene-based substance is preferably controlled to be less than 50 ⁇ m, and more preferably the D90 index is controlled to be 30 ⁇ m or less, more preferably 5 to 25 ⁇ m. Between, for example, it can be 45um, 40um, 35um, 30um and so on.
  • the control of D90 index below 70 ⁇ m means that the particle size below 100um accounts for 90% of the whole, that is, the maximum particle size of 90% is 100um, which ensures the dispersibility of graphene and ensures the graphene particles.
  • the uniformity of size avoids the occurrence of particle agglomeration.
  • the D90 index of the graphene-based substance is preferably controlled to 20 times or less, preferably 10 times or less, more preferably 5 times or less, or 8 times or less, 11 times or less, 12 times or less, or 13 times, of the D10 index. Less than or less than 14 times.
  • the purpose of this is to Try to maintain the large structure of graphene materials, ensure that graphenes do not agglomerate between layers, and prevent the problem of stress concentration point breakage caused by graphitic materials with different diameters, because the particle size is too large or too small. It is not conducive to the formation of a uniform substance with nanocellulose, so that the performance of all aspects of the composite nanocellulose product is excellent, so it is better to control the particle size index of the graphene material within a suitable range.
  • the specific control of graphene D90, D10 indicators need to adopt a graded pretreatment method, including: mixing graphene materials with deionized water, leaving the bottom precipitate after centrifugation at 2000-3000 rpm.
  • the supernatant liquid is centrifuged at 5000-7000 rpm to obtain a second bottom precipitate and a secondary supernatant, respectively, wherein the fractionated centrifugation liquid comprises a bottom sediment, a secondary bottom precipitate, and a secondary supernatant. It is preferred to have a secondary bottom precipitate.
  • the rate of centrifugation of the bottom precipitate is relatively low, and the rate of further centrifugation of the supernatant is relatively high, because the particle size of the precipitate is generally large, and if the rate is too fast, it is not conducive to the deposition of large particles.
  • the particle size of the supernatant is generally small, so the rate needs to be faster so that the less granular material is present in the supernatant.
  • Such graphene materials with relatively uniform particle size are classified and precipitated at the bottom, or precipitated at the second bottom, or in the secondary supernatant.
  • the fractionated centrate can select any of the above-mentioned classified materials.
  • Graphene materials with uniform particle size can be ensured, and the size of the particles is also suitable, so as to ensure the uniformity of the film diameter, which is beneficial to the subsequent performance of the prepared product.
  • the time of centrifugation operation at 2000-3000 rpm is preferably controlled between 20-40 min, and the time of centrifugation operation at 5000-7000 rpm is preferably controlled between 10-30 min, and the control is more favorable in better operation time.
  • the particle size fractionation treatment is more thorough, so that the particle size distribution is more uniform.
  • the main purpose of the ultrasonic dispersion treatment is to achieve the effect of separation and degradation by mechanical dispersion and ultrasonic cavitation effect, and the time of the ultrasonic dispersion treatment is preferably controlled at 15-60 min, more preferably 30. -50min, the power of the ultrasonic dispersion treatment is preferably controlled between 500-1500kw, more preferably between 1000-1200kw.
  • a certain grinding operation is generally performed before the ultrasonic dispersion treatment, depending on The mutual friction between the grinding beads and the fibers achieves the effect of separating and degrading the fibers, which also correspondingly improves the overall working efficiency.
  • the grinding frequency is preferably controlled between 25-35 Hz, more preferably between 27-32 Hz.
  • the grinding time is preferably controlled between 4 and 6 h, more preferably between 5 and 5.5 h.
  • the graphene material used is preferably subjected to a certain grinding pretreatment before being mixed with the cellulose and deionized water, and more preferably, only the wall of the container after the pretreatment is used. Residual graphenes, mixed with cellulose and deionized water. Since the graphene on the wall of the vessel has better nano-characteristics and a lamellar structure, the graphene-like substance on the wall of the vessel is more preferably selected.
  • the concentration of cellulose is preferably controlled between 1% by weight and 10% by weight, more preferably between 2% by weight and 8% by weight, and may be other than 3wt%, 4wt%, 5wt%, 6wt. %, 7wt%, etc.
  • the method for preparing graphene composite nanocellulose according to the embodiment of the invention improves the efficiency of the grinding itself and shortens the grinding time by adding the graphene material, especially the use of biomass graphene to make the nanocellulose have antibacterial inhibition The functions of bacteria and far infrared are more prominent.
  • the graphene composite nanocellulose prepared by the above preparation method further doubles the mechanical properties of the nanocellulose itself, and additionally imparts excellent antibacterial properties, far infrared properties, excellent toughness, hot water resistance and the nanocellulose.
  • Antistatic performance widely used, has a wide range of applications in pharmaceutical, environmental protection, food packaging, composite materials.
  • the invention also provides a method for preparing nano cellulose, which solves the problems of high energy consumption, serious environmental pollution and easy agglomeration of nano cellulose.
  • the present invention provides the following technical solution: a method for preparing nanocellulose, comprising the following steps:
  • the graphene-based substance is selected from the group consisting of graphene and its derivatives, graphene oxide and its derivatives One or more of the biomass, biomass graphene, and derivatives thereof, preferably graphene oxide/biographene.
  • the above method utilizes a sheet-like structure of a graphene substance to be inserted into an amorphous region in cellulose, and disperses it into a uniformly dispersed nano-scale structure, and the friction of physical grinding is more advantageous for graphene-based materials and fibers.
  • the contact of the element, and the cutting effect of the graphene sheet structure is further realized by grinding external force.
  • the above method of the present invention prevents the nanocrystalline cellulose from agglomerating by cutting to form nanocrystalline cellulose, and then utilizing the physical barrier action of the graphene to form a nanocrystalline cellulose which is stable in performance and easy to transport.
  • the present invention does not require strong mechanical force or high temperature reaction, and thus has low energy consumption and no environmental pollution.
  • the biomass graphene according to the present invention is a monolayer graphene, a small layer graphene, a graphene nanosheet layer structure prepared by a catalytic or carbonization process using biomass resources as a main raw material, and is loaded with metal/non-metal.
  • a composite carbon material of a metal element is a monolayer graphene, a small layer graphene, a graphene nanosheet layer structure prepared by a catalytic or carbonization process using biomass resources as a main raw material, and is loaded with metal/non-metal.
  • the graphene oxide according to the present invention may be a commercially available graphene, or may be a product of oxidation of graphene prepared by partial reduction crosslinking, or may be an oxidized product of graphene prepared by PECVD. It is a graphene oxide produced by other methods.
  • the graphene oxide derivative comprises any one or a combination of at least two of elemental doped graphene oxide or functionalized graphene oxide.
  • the element-doped graphene oxide comprises any one or a combination of at least two of metal-doped graphene oxide or non-metal element-doped graphene oxide.
  • the metal-doped metal element typically, but not limited to, includes potassium, sodium, gold, silver, iron, copper, nickel, chrome titanium, vanadium or cobalt.
  • the non-metallic element doped graphene typically includes, but is not limited to, nitrogen, phosphorus, sulfur, silicon, boron or silicon.
  • the non-metal element doped graphene oxide comprises any one or a combination of at least two of nitrogen-doped graphene oxide, phosphorus-doped graphene oxide or sulfur-doped graphene oxide.
  • the functionalized graphene oxide comprises graphene oxide grafted with a functional group.
  • the functionalized graphene oxide comprises graphene oxide grafted with any one or a combination of at least two of a hydroxyl group, a carboxyl group or an amino group.
  • the hydroxyl group of the present invention includes -R1-OH, and the R1 includes an alkane group, and a typical but non-limiting hydroxyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or the like. .
  • the carboxyl group of the present invention includes -R2-COOH, and the R2 includes an alkane group, and a typical but non-limiting hydroxyl group may be a methyl group.
  • the amino group of the present invention includes -R3-NH3, and the R3 includes an alkane group, and a typical but non-limiting hydroxyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or the like. .
  • the graphene derivative and the biomass graphene derivative are the same as the above graphene oxide derivative.
  • the graphene-based substance is added in an amount of 5 wt% or less, preferably 2 wt% or less, preferably 1 wt% or less, more preferably 0.6 wt% or less, of the aqueous solution of the cellulose precursor.
  • the graphene-like substance has a particle size of ⁇ 30 ⁇ m, preferably ⁇ 15 ⁇ m, preferably ⁇ 3 ⁇ m, preferably ⁇ 500 nm, preferably ⁇ 100 nm, and may be 28 ⁇ m, 25 ⁇ m, 20 ⁇ m, 10 ⁇ m, 5 ⁇ m, 2 ⁇ m, 1 ⁇ m, 200 nm and the like.
  • the cellulose is selected from one or more of a mixture of lignocellulose, corncob cellulose, microcrystalline cellulose, bacterial cellulose, pulp.
  • the pulp is selected from the group consisting of bleached wood pulp, bleached straw pulp, corn core pulp, cotton pulp, hemp pulp, bamboo pulp, mash pulp, dissolving pulp, rag pulp, unbleached wood pulp, and unbleached straw pulp.
  • the grinding according to the present invention does not require the same high requirements as the conventional mechanical method. Since graphene is a two-dimensional material, it has the effects of enhancing the lubricating effect and reducing the friction. Therefore, the introduction of graphene by the grinding process is more advantageous for grinding. The effect is to reduce energy consumption. If the grinding force is too large to favor the action of graphene, the preferred grinding conditions are:
  • Dispersing treatment at a stirring speed of 1000 to 13600 rpm for 1 to 30 minutes, preferably at a stirring speed of 1000 to 3000 rpm for 10 to 20 minutes using an ultrasonic homogenizer having a power of 200 to 400 W; or using a mechanical stirrer or a magnetic stirrer
  • the mixture is continuously stirred at a rate of 300 to 500 rpm for 1 to 72 hours, preferably for 1 to 3 hours.
  • the polishing temperature is 4 to 50 ° C, and more preferably 4 to 10 ° C.
  • the present invention can also combine chemical measures such as acid hydrolysis and TEMPO catalytic oxidation to improve production efficiency.
  • chemical measures such as acid hydrolysis and TEMPO catalytic oxidation to improve production efficiency.
  • an acid is added for acid hydrolysis before or during the grinding:
  • TEMPO catalytic oxidation system is additionally added to the oxidation treatment before or during the grinding:
  • the reaction is stirred at a pH of 10 to 11, 10-40 ° C for 2 to 24 hours under the action of a TEMPO catalytic oxidation system;
  • the catalytic oxidation time is not strictly limited, and generally, depending on the degree of the reaction, for example, when the hydroxyl group is depleted, the catalytic oxidation reaction is terminated, and the consumption of the hydroxyl group may be controlled according to the time.
  • the TEMPO catalytic oxidation system can oxidize some or all of the hydroxyl groups of the cellulose to a carboxyl group, and can also catalyze the oxidation of a hydroxyl group or an epoxy functional group of a graphene substance to a carboxyl group.
  • the TEMPO system partially oxidizes the non-crystalline regions of cellulose into macromolecular structures and allows the crystallization regions to open apart from each other, but also facilitates the shearing of graphenes.
  • graphite is passed through the TEMPO system.
  • the hydroxyl group of the olefinic substance is also oxidized to a carboxyl group, which reduces the thickness of the graphene and is more favorable for the shearing action of the graphene-based substance.
  • the TEMPO catalytic oxidation system is an aqueous system containing TEMPO and/or its derivatives, hypochlorite, bromide and/or perchlorate; more preferably TEMPO, sodium hypochlorite, sodium bromide and / or aqueous solution of sodium perchlorate;
  • the TEMPO derivative is selected from the group consisting of 2-azaadamantane-N-oxyl, 1-methyl-2-aza-adamantane-N-oxyl, 1,3-dimethyl-2-nitrogen
  • 2-azaadamantane-N-oxyl 1-methyl-2-aza-adamantane-N-oxyl, 1,3-dimethyl-2-nitrogen
  • 2-hydroxy TEMPO derivative 4-hydroxy TEMPO derivative
  • the TEMPO and/or its derivative is added in an amount of 0.05% to 5% by weight, preferably 0.1% to 3%, more preferably 0.3% to 2%, still more preferably 0.5% to 1%; %, 0.3%, 0.8%, 1%, 1.2%, 1.5%, 2.5%, 3.5%, 4%, 4.5%, etc.;
  • the hypochlorite is added in an amount of 10% to 500%, preferably 30% to 95%, more preferably 40% to 75% by weight of the cellulose; 50%, 70%, 100%, 120%, 135%, 160%, 200%, 300%, 400%, 450%, etc.;
  • the bromide salt and/or perchlorate is added in an amount of 0.5% to 50%, preferably 10% to 30%, more preferably 3% to 20%, still more preferably 5% to 10% by weight of the cellulose; 3%, 8%, 10%, 12%, 15%, 18%, 25%, 35%, 45%, etc.;
  • the hypochlorite is added at a concentration of from 5 to 15% by weight.
  • the nanocellulose aqueous solution is subjected to solution removal, washing, and drying;
  • the solution removal comprises centrifugation, filtration or a combination thereof;
  • the drying comprises vacuum drying, freeze drying, air drying, microwave drying, spray drying, infrared drying, high frequency drying or a combination thereof; preferably, the drying is freeze drying.
  • the drying conditions have an important influence on the stability of the product.
  • the product is frozen at -20 to -25 ° C for 10 to 20 hours, and then placed in a cold trap of a freeze dryer for pre-preparation.
  • the freezing and freezing dryer has a cold trap temperature of -50 to -80 ° C; after the pre-freezing, it is freeze-dried at a vacuum of 1 to 10 Pa for 24 to 48 hours.
  • the graphene composite of the present invention is very easy to disperse in a solvent and is not easily agglomerated, even without the aid of an ultrasonic or dispersing agent.
  • the high-performance graphene composite nanocellulose provided by the invention can maintain a high content of graphene materials, the graphene particles are still uniformly dispersed, the particle size is relatively uniform, the agglomerated particles are less produced, and the properties are stable;
  • the preparation method of the high-performance graphene composite nanocellulose of the invention has a close connection before and after, and the method is simple and quick, and no chemical agent such as acid and alkali is used in the whole preparation process, and the environment is green and has no waste.
  • the production of acid waste alkali, and the preparation method of the present invention also achieves the advantages of using acidification to prepare nanocellulose, such as a suitable aspect ratio.
  • the preparation method has the advantages of simple and easy operation, mild operating conditions, industrialized production of graphene composite nanocellulose, and good economic benefit;
  • the high-performance graphene composite para-aramid fiber of the invention has a wide application and has wide application in various industries such as medicine, environmental protection, food packaging and composite materials.
  • the prepared nanocellulose has an aspect ratio of 100 or more, especially 200 or more, or even 300 or more; and the diameter can reach 20 nm or less, especially 10 nm or less, or even 5 nm or less.
  • the preparation method has low energy consumption and no environmental pollution.
  • Biomass graphene A The preparation method is Example 4 of Chinese Patent Publication No. CN105502330A.
  • Biomass graphene B The preparation method is Example 7 of Chinese Patent Publication No. CN104016341A.
  • Biomass graphene C The preparation method is Example 1 of Chinese Patent Publication No. CN104724699A.
  • Graphene F Model produced by Changzhou Sixth Element Materials Technology Co., Ltd.: SE1430.
  • Graphene oxide G Model produced by Changzhou Sixth Element Materials Technology Co., Ltd.: SE2430W.
  • Example 2 The difference from Example 1 was that 0.001 g of corncob nanocellulose having a diameter of 5-10 nm and an aspect ratio of 20-30 (the nanocellulose content in the solution was 1.5 wt%) was added.
  • Example 2 The difference from Example 1 was that 0.005 g of corncob nanocellulose having a diameter of 3-5 nm and an aspect ratio of 15-20 (the nanocellulose content in the solution was 2.5 wt%) was added.
  • Example 2 The difference from Example 1 was that 0.03 g of corncob nanocellulose having a diameter of 12-15 nm and an aspect ratio of 10-15 (the nanocellulose content in the solution was 0.5 wt%) was added.
  • Example 2 The difference from Example 1 was that 0.05 g of corncob nanocellulose having a diameter of 1-3 nm and an aspect ratio of 80-100 (the nanocellulose content in the solution was 1.5 wt%) was added.
  • Example 2 The difference from Example 1 was that 0.1 g of corncob nanocellulose having a diameter of 20 to 25 and an aspect ratio of 5 to 10 (having a nanocellulose content of 1.5 wt% in solution) was added.
  • Example 1 The difference from Example 1 is that the corncob nanocellulose is replaced with wood nanocellulose and cotton nanocellulose.
  • Example 1 The difference from Example 1 is that biomass graphene A is replaced with biomass graphene B, biomass graphene C, graphene D, graphene E, graphene F, and graphene oxide G, respectively.
  • Example 2 The difference from Example 2 is that TEMPO catalytic oxidation treatment is performed on the biomass graphene A.
  • the specific steps are as follows: a. Take 1 g of biomass graphene A, add 200 g of water to stir to form a uniform slurry, and then add TEMPO catalytic oxidation combination. The reaction (0.01 g TEMPO, 1 g sodium hypochlorite, 0.05 g sodium bromide) was stirred, and the pH of the reaction system was maintained in the range of 10.5-11 by adjusting with 0.5 wt% sodium hydroxide solution and 1 wt% glacial acetic acid solution. After the change, the reaction was stopped to obtain a suspension, and the reaction time was 2.5 h; b.
  • the suspension obtained in the step a was filtered, and washed repeatedly with water, and centrifuged at a speed of 1000 rpm, each time of centrifugation for 5 minutes, and finally The pH of the suspension was neutral after washing, and dried to obtain a modified graphene powder.
  • Example 1 The difference from Example 1 is that 1 g of biomass graphene A is taken in step (1) and added to 0.01 g of corncob nanocellulose having a diameter of 3-5 nm and a length to diameter ratio of 15-20 (the nanocellulose content in the solution is 2 wt. Stirring was continued for 30 min in an aqueous solution of %).
  • Example 2 The difference from Example 1 is that the grinding step is increased before the drying of the step (2), as follows:
  • the product and the distilled water were mixed into a solution at a mass ratio of 1:10, and subjected to dispersion treatment at a stirring speed of 10,000 rpm for 30 minutes at a normal temperature using an ultrasonic homogenizer having a power of 400 W.
  • Example 2 The difference from Example 1 is that the step of (2) is increased before the drying step, as follows:
  • the product was made into a solution with distilled water at a mass ratio of 1:1000, and continuously stirred at a temperature of 500 rpm for 72 hours at room temperature using a mechanical stirrer.
  • Biomass graphene A, biomass graphene B, biomass graphene C, graphene D, graphene E, graphene F, and graphene oxide G, respectively, without nanocellulose were used as comparative examples.
  • the modified graphene powder obtained in Example 1-18 and the graphene-like substance in the comparative example were directly dispersed in water and ethanol solution, respectively, without any dispersing agent, and ultrasonicated for 20 min, and the specific operation was as follows:
  • Example 1 It was found through further experiments that the graphene composite powder obtained in Example 1 was dispersed in water, and the maximum dispersion amount without precipitation for 24 hours was 5% by weight.
  • the solution obtained in the step (1) was ultrasonically centrifuged to collect a precipitate. Then, the precipitate is frozen at -20 to -25 ° C for 10 h, and then placed in a cold trap of a freeze dryer for pre-freezing, and the cold trap temperature of the freeze dryer is -70 to -80 ° C; After the end of the freezing, it was freeze-dried at a vacuum of 1 Pa for 24 hours to obtain a nanocellulose solid.
  • Example 2 The difference from Example 1 is that the solid content of the biomass graphene A in the aqueous solution in the step (1) is 0.05 g, 0.2 g, 0.5 g, 0.7 g, 1 g.
  • Example 19 The difference from Example 19 was that the grinding method of the step (1) was different: continuous stirring was carried out at a temperature of 500 rpm for 3 hours at room temperature using a mechanical stirrer or a magnetic stirrer.
  • Example 19 The difference from Example 19 was that the grinding method of the step (1) was different: continuous stirring was carried out at a temperature of 400 rpm for 20 hours at room temperature using a mechanical stirrer or a magnetic stirrer.
  • Example 19 The difference from Example 19 is that biomass graphene A is replaced with biomass graphene B, biomass graphene C, graphene D, graphene E, graphene F, and graphene oxide G, respectively.
  • Example 19 The difference from Example 19 was that the corncob cellulose was replaced with lignocellulose, bleached wood pulp, respectively.
  • the solution obtained in the step (1) was ultrasonically centrifuged to collect a precipitate. Then, the precipitate is frozen at -20 to -25 ° C for 10 h, and then placed in a cold trap of a freeze dryer for pre-freezing, and the cold trap temperature of the freeze dryer is -70 to -80 ° C; After the end of the freezing, it was freeze-dried at a vacuum of 1 Pa for 24 hours to obtain a nanocellulose solid.
  • the aspect ratio, diameter, and degree of agglomeration of all of the above examples were tested and the results are shown in Table 3.
  • the test method for the degree of agglomeration is as follows: 1 g of the solid nanocellulose prepared in the example is added to 30 g of the aqueous solution, and the sedimentation time is observed after a simple physical stirring.
  • the preparation method of the bleached corncob cellulose is as follows: 1) acid hydrolysis of the corn cob raw material is first performed, and the pentose solution and the sulfuric acid hydrolysis residue are obtained after separation; the acid amount is 6 wt% of the corn cob raw material, and the hydrolysis temperature is 130 ° C, time. 2h; then the above acid hydrolysis residue is treated with sodium hydroxide solution, and the alkali solution and the alkali residue are obtained after separation.
  • the amount of the alkali is 7 wt% of the corn cob raw material, the treatment temperature is 90 ° C, and the time is 3 h; 2)
  • the above-mentioned alkali hydrolysis residue is bleached, and the treatment method is hydrogen peroxide bleaching, the amount of hydrogen peroxide is 6 wt% of the dry weight of the alkali residue, the slurry concentration is 10 wt%, the temperature is 90 ° C, the bleaching time is 2 h, after the above purification treatment Corncob cellulose can be obtained, the main indicators of which are whiteness of 75% and fiber length of 0.16 mm.
  • the preparation method of high performance graphene composite nanocellulose is as follows:
  • the preparation method of high performance graphene composite nanocellulose is as follows:
  • the preparation method of high performance graphene composite nanocellulose is as follows:
  • the preparation method of high performance graphene composite nanocellulose is as follows:
  • the specific process steps are substantially the same as those of the embodiment 40, and the difference from the embodiment 40 is that the selected graphene oxide fractionated centrate is the first bottom precipitate (D90 is 70 um, D10 is 30 um).
  • the specific process steps are substantially the same as those of the embodiment 40, and the difference from the embodiment 40 is that the selected graphene oxide fractionated centrate is the first bottom precipitate (D90 is 370 um, D10 is 120 um).
  • the specific process steps are basically the same as those of the embodiment 40, and the difference from the embodiment 40 is that the selected graphene oxide fractionated centrate is the second supernatant (D90 is 20 um, and D10 is 0.5 um).
  • the specific process steps are basically the same as those of the embodiment 40, and the difference from the embodiment 40 is that the selected graphene oxide fractionated centrate (30 um for D90 and 10 um for D10).
  • Example 40 The specific process steps are substantially the same as those of Example 40, and the difference from Example 40 is that the selected graphene oxide fractionated centrate (590 for D90 and 0.25um for D10).
  • Example 40 The specific process steps are substantially the same as in Example 40, and the difference from Example 40 is that the selected graphene oxide fractionated centrate (25 um for D90 and 5 um for D10).
  • the specific process steps are basically the same as those in the embodiment 40, and the difference from the embodiment 40 is that the selected graphene oxide fractionated centrate (D90 is 70 um, D10 is 20 um).
  • Example 44 The difference from Example 44 is that in the step 1), the graphene oxide is replaced with the biomass graphene.
  • Example 44 The difference from Example 44 is that in the step 1), the graphene oxide is replaced with redox graphene.
  • Example 44 The difference from Example 44 is that in the step 1), the graphene oxide is replaced by a mixture of nitrogen-doped graphene and graphene oxide (mass is 1:1).
  • Example 40 The difference from Example 40 is that in the step 1), 10 g of graphene oxide, 390 g of corncob cellulose, and 13 L of deionized water.
  • Example 40 The difference from Example 40 is that in the step 1), 10 g of graphene oxide, 990 g of corncob cellulose, and 99 L of deionized water.
  • Example 40 The difference from Example 40 is that in the step 1), 10 g of graphene oxide, 2000 g of corncob cellulose, and 40 L of deionized water.
  • step 1) the corn cob cellulose obtained in Preparation Example 1 was replaced with corn cob cellulose which was not purified and purified.
  • Example 40 The difference from Example 40 is that in the step 1), the corn cob cellulose obtained in the preparation example was replaced with poplar cellulose.
  • Example 40 The difference from Example 40 is that in the step 1), the corn cob cellulose obtained in the preparation example was replaced with reed cellulose.
  • the diameter of the prepared nanocellulose is more nanometerized, and the aspect ratio is larger and fluctuates within a certain range, which is more favorable for subsequent applications.
  • the graphene composite nanocellulose prepared in Examples 44 and 48 of the present invention was respectively replaced with Patent Publication No. CN102344685A, and the name is "a method for preparing a nanocellulose microfiber reinforced polymer composite material".
  • the nanocellulose materials used in the preparation or the preparation process thereof are as follows:
  • Example 1 The tensile strength of the composite film was 47 MPa, the tensile modulus was 1.5 GPa;
  • Example 2 The strength of the composite fiber was: 4.5 cN/dtex;
  • Example 3 The strength of the composite fiber was: 5.5 cN/ Dtex;
  • Example 4 The tensile strength of the composite film reached 150 MPa, the tensile modulus reached 4.6 GPa;
  • Example 5 The strength of the composite fiber was 4.3 cN/dtex;
  • Example 6 The strength of the composite fiber was: 6.4cN/dtex.
  • Example 1 The tensile strength of the composite film was 49 MPa, the tensile modulus was 1.7 GPa;
  • Example 2 The strength of the composite fiber was: 4.8 cN/dtex;
  • Example 3 The strength of the composite fiber was: 5.9 cN/ Dtex;
  • Example 4 The tensile strength of the composite film reached 160 MPa, the tensile modulus reached 4.9 GPa;
  • Example 5 The strength of the composite fiber was 4.6 cN/dtex;
  • Example 6 The strength of the composite fiber was: 6.7cN/dtex.
  • the invention solves the problems that the existing graphene composite is easy to disperse in the solvent, easy to agglomerate, etc., wherein the high-performance graphene composite nanocellulose preparation method is environmentally friendly and easy to operate, and the prepared graphene nanocellulose is widely used. It has a wide range of applications in many industries such as medicine, environmental protection, food packaging and composite materials.

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Abstract

La présente invention concerne un composite de graphène, son procédé de préparation et son utilisation, un procédé de préparation de nanocellulose et la nanocellulose résultante, et une nanocellulose composite de graphène à haute performance et son procédé de préparation. Le composite de graphène comprend de la nanocellulose et une substance de graphène, au moins une partie de la nanocellulose étant insérée dans la substance de graphène. Le composite de graphène est facilement dispersé dans un solvant et ne s'agglomère pas facilement, même sans l'aide d'ultrasons ou d'un dispersant. Le procédé de préparation de nanocellulose consiste à : ajouter une substance de graphène à une solution aqueuse de cellulose pendant un processus de broyage. La présente invention résout les problèmes de consommation d'énergie élevée, de pollution environnementale lourde et d'agglomération facile de la nanocellulose. La nanocellulose composite de graphène à haute performance est principalement constituée de nanocellulose et d'une substance de graphène qui se portent in-situ l'une l'autre, dans laquelle la substance de graphène a un contenu élevé, est dispersée de manière uniforme, présente des particules ayant une taille uniforme et quelques particules agglomérées, et a également d'autres excellentes performances.
PCT/CN2017/100249 2016-09-20 2017-09-01 Composite de graphène, son procédé de préparation et son utilisation, procédé de préparation de nanocellulose et nanocellulose résultante, et nanocellulose composite de graphène à haute performance et son procédé de préparation WO2018054212A1 (fr)

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